Zirconyl 2-ethylhexoate



United States Patent 2,739,905 ZIRCONYL Z-ETHYLHEXOATE Gerry P. Mack, Jackson Heights, New York, N. Y., assignors, by Carlisle Chemical Works, Inc., poration of Ohio No Drawing. Application August 29, 1952, Serial No. 307,153

6 Claims. (Cl. 106-310) and Emery Parker, mesue assignments, to Reading, Ohio, a cor- The invention relates to new organic zirconylic compounds, which are useful in drier compositions for drying oils.

Zirconium naphthenate and the zirconium soaps of the higher use for commercial or We have found that of zirconylic acid technical applications. the 2-ethylhexoic acid derivatives have excellent drying properties and The new driers can be prepared by the double decomposition of water soluble zirconium salts, for instance zirconium oxychloride or zirconium sodium sulfate, with an alkali Z-ethylhexoate or by the fusion of a water in- After removing unreacted 2-ethylhexoic acid, the obtained reaction product corresponds to the empirical formula:

C4H9CH C2H5 C0O-(2!O )nOC(CZH5)HCC4H0 wherein n is a fractional number between 1 and 2.

The reaction product represents a mixture or complex of two zirconylic acid compounds:

(2) O=Zr[OOCCH(C2H5)C4H9]a Molecular weight: 393 .6 Zirconium=23 .17% and Molecular weight: 516.8 Zirconium=35 .3

The value of n in Formula 1 depends on the ratio of these two compounds (2) and (3) in the reaction product. We were not able to separate the product (1') into ently identical solubility properties The ratio of (2) to (3),

in various solvents. however, can be varied and depends on the conditions of the reaction, the temperature of drying and other factors. For instance, if the product is prepared by a double decomposition reaction at temperatures exceeding 100 changed to 40:60.

If a solution of the anol and then distilled compound is extracted with methunder reduced pressure, the result- 2,739,905 Patented Mar. 27, 1956 ing product has almost entirely the composition of Formula 3. Also this product is still completely soluble in hydrocarbons. If the Zr content of the products is raised than 35.3 per cent, i. e. beyond the dimer of no value for the use as driers.

The following examples are given to illustrate the preparation and characteristics of the new compound.

Example 1 To .5 mol of zirconium oxychloride containing 8 mols of crystal water dissolved in 200 cc.

tent 66.6 per cent; therefore, it corresponded to the formula 1 with n=l.32.

Example 3 1 mol (=385 g.) of sodium zirconium sulfate was dissolved in 800 cc. of water. To the clear solution was added 1 mol of dry sodium carbonate dissolved in A suspension of basic zirconium carbonate was formed, and 1.8 mols of Z-ethylhexoic acid were slowly added from water and filtered from impurities; then, was removed under reduced pressure. The obtained zirconyl compound contained 25.5 per cent of zirconium and 69 per cent of 2-ethylhexoic acid. This compound was redissolved in toluol, and methanol was added to methanol no separation took place in the upper layer.

The lower toluol layer whichconfiincd-almostentirt'ibflhe zirconyl compound was separated-andthetoluolremoved by distillation. The white solid residuewas again digested with hot methanol and a powdery solid was obtained which contained 34.15 percent of zirconium and 56.2 per cent of Z-ethylhexoic acid and consisted-esentially of thedimeric compound (3'). The product is perfectly soluble in hydrocarbon solvents. t

Example 4 ASTMLlnseed Oil, g.. 100 100 100 100 100 100 Manganese Metal, percent 0.03 0.025002 0.0% 0.01 0.005 0.0 ZirconiumMetaLperuent. 0.0 0.005 0.01 0.015 0.02 0.025 0.03 Drying'Time,min.- 300 300 300 300 308 330 over 720 ASTM Linseed Oil,'g- 100 100 100 100 100 1100 100 Cobalt Metal, percent" 0.03 0.025 0.020 0.015 0.010 0.4105 11.0 Zirconium Metal, percent Drying Time,min 240 240 240 245 270! 420 over-720 If the same amounts of manganese and cobalt are used as in above tables, but without zirconium the following results are obtained:

60 per cent metal in mineral ASTMllnseed 0il,g .10, m0 100 .100. .100 Manganese Metal, percent...- 0.03 0.025 0102 '0.'0I5 0.010 Drying Time, percent......... .300 1310 A205 .mzerm ASTM linseed oil,

g 100 100 100' '100 100 100 100 Cobalt Metal, percent 0.03 0.025 0.020 0.01s :0. 010 0005 Drying Time, min.- 240. 265 300 360 00015120 In view of the fact that zirconium l-ethylhexoate alone i in even larger amounts as indicated .in abouetablesdoes not produce a dry oil .film, and the oil films are tacky even after 24 hours, the enhancing. action of the zirconium 2-ethylhexoate is clearly demonstrated. 7

As will be noted on consideration of the tables, :the useful mixtures contain a ratio of about 5 to 80 per cent of Zr to 95 to 20 per cent of Mn and of about 5 to 60 per cent of Zr to 95 to 40 percent of Co, calculated on the metal content.

' 4 Example 5 Compositions containing the desired amount of zirconyl i Z-ethylhexoate combined with manganese and/or cobalt Z-ethylhexoate can be prepared as follows: 231 g. (0.6 mol) of sodium zirconyl sulfate and 62 g. (0.4 mol) of cobaltous sulfate are dissolved in 800 cc. of cold water. 288.4 g. (2 mol) of .Z-ethylhexoic acid neutralized with 80 g. of caustic soda in 300cc. of water are added under stirring to =thesulfate solution; the precipitate is washed with cold water and .then with cold methanol.v The obtained composition can :be worked t p-directly .to a drier solution containing the desired drier concentrations and ratios for-use as described in Example :4. For this purpose the composition is dissolved :in mineral spirits, dehydrated by heating to about 120 .Cmand filtered. The filtered solution is then diluted with mineral spirits to a content of 6% metal in the form of 3.6% of zirconium and 2.4% of cobalt.

In an identical manner the mixedzmanganeseiziirconium Z-ethylhexoate can be prepared containing after dilution 4.3% of zirconium and 1.2% of manganesq orwhateuer ratios .are desired.

What-we claim is:

1. As a new composition of matter, a mixture comprising manganese 2-ethylhexoate and zirconyl Z-ethylhexoate in ;.a ratio of about 95 to 20 .per cent of .Mnzto about '5 to :80 per cent of Zr, calculated on the metal :content by weight.

.2. .As :a .new composition of matter, .a mixture com prising :cobal't. Z-ethylhexoate and zirconyl Z-ethylhexoate in a ratio of about 95 to 40 per cent'of tCo to about 5 to .per cent of Zr, calculated on the :metal content iby weight.

.3. As :a new composition of matter, a mixture cornprisingzirconyl 2-ethylhexoate, manganese'2ecthylhexoate and cobalt .Z-ethylhexoate in a ratio of about 5 to per cent of into about to 25 per cent 'of combined Z Mnrand-Co, calculated on the metal content .by weight.

4. As a new composition of matter, useful in drier compositions for drying oils, zirconium compounds of 2-ethylhexoic acid, in which Z-ethylhexo'ic acid radicals are bound to "the zirconyl :group .=Zr.--O.

.5. As a -.new composition of matter, useful in drier compositions for drying oils,'zirconyl 2-ethy1 hexoate of the formula 6. As a new composition of matter, the dizirconyl derivative of 2-ethylhexoic acid of the formula References Cited in the file of .this patent UNITED STATES PATENTS 

1. AS A NEW COMPOSITION OF MATTER, A MIXTURE COMPRISING MANGANESE 2-ETHYLHEXOATE AND ZIRCONYL 2-ETHYLHEXOATE IN A RATIO OF ABOUT 95 TO 20 PER CENT OF MN TO ABOUT 5 TO 80 PER CENT OF ZR, CALCULATED ON THE METAL CONTENT BY WEIGHT. 